DE1645989A1 - Process for the preparation of substituted oxazole compounds - Google Patents

Description

OS. 1. M. MAA S DR. WG PFEIFFER f AT E NTAM WA IT c

46Q a MOMCHEH 23

* * UNGESS8STS. 29 - TlL 3430 jo

American Cyanamid Company, Wayne, Lew Jersey, V.St.A. Process for the preparation of substituted oxazole compounds Addition to patent ....... (patent application A 48 028 ΐνα / ΐ2ρ)

The invention relates to the further development of the method according to patent. ... ... (patent application A 48 028 Γ? Ϊ́ | / Ι2ρ).

The main patent relates to a process for the preparation of 2-atyryloxaxol compounds by reacting 2-methylbenzoxmzene or 2-methylnaphthoxazole, which can be substituted by lower alkyl or alkoxy groups, hydroxyl, carboxyl, cyano or nitro groups or halogen atoms with benzaldehyde or naphthalenaldehyde duroh lower alkyl or alkoxy groups, hydroxyl, carboxyl, cyano or nitro groups or halogen atoms can be substituted, in the presence of dehydrating agents and an inert solvent at the temperature of the fire, removing the water of condensation from the reaction mixture and recovering the formed 2-Styrylox _a zols from de · Reaktlonsgemlsoh, characterized by the fact that the reaction is carried out in

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Presence of a sulfonic acid and a dialkyl derivative Foraaald or Aoetaali ait lower * AlkylgruppendurhhfUtirt ·

Surprisingly, it would be found that a "combination of the ketalytiach effective means can be achieved by a catalyst which consists of a Jewonlu - or AaIn" as an arylaulfonic acid _: 7

t ; ..: ■■: ■■. ■■ "'" ■ ■.: - .. ./. "■"'-: -. ■■■

laoh de «invention-alSen process, a molar part of the methyl

old little · tan · 1 mol partially de · aldehydes in a · inerts Löaungaalttel In the presence το η about 10 to 15% elnea Aaeonlua- or Aalnaalaea a ArylaulfonaÄure, beaogen on daa Gewloht the Beaktlonatelinehaer, for a suitable period of time uageaetst, Daan is the Beaktloneaiaohung In waeaer, among other things buy the product.

Aaa alndcatena 1 mole of aldehyde per mole of Oxasol is required for the solution. of about 10 to 50 %, voriugawelae of about 10 to 30 % over the etöohioaetrlaoh required amount used. Higher overhaul do not result in any further amendment of the procedure and alnd unbelievably

ΊΑ · öaaetaung is durohgefOhrt at RUokflueteaperatur, d _o h at "boiling point de · · LOaungaalttel or in the beginning," baohnitt de · muddled formed Axeotropa ouch Waeaer and Löaungaelttel · During dea ROckflulaledens is daa Waaaer, daa in üeeetsung

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is formed and contained in the fluid bowl. The formation τοη Wa · β leaves an indication for the fact that the action takes place, and the end of the water formation means that the use can end. To achieve satisfactory results, water is required to remove the amount of water that has formed. They are required for a complete explanation · Since in certain circumstances it depends on the "respective" leektloas · tellnehaera, tea and the Luaungealttel, the Eflokflulteap * - ratur, the Oröie dta AnMtsee and ί · χβ; 1 · 1 · βηβο * ^b * ² ^ * <* ^^ can therefore eel Durohftthrtuig the Oneetiung ta technleohen MeSetae etva Ιθ - 30 hours © and when carried out in Leboratorlaatentetnb about 5 ble 8 hours, separating "en beieYlelevele · et« · 3000 f BeeJttlonetellneojier old Xβgeslτβel · LOetη det and the Mokflttietenperetar during the Indabeohnitte 163 ⁰ O erreloht, the Beektloneseit "tt" 5.5 Stand ·

2u the ArylettlfoneÄuren, the gate production of the Anewnitei- or Aalneelie for the inventions Sveoke Terwenaet verde · kSnnem «GenOren belepielewelee aneubstitulerte and C | - Uo C ^ Q-eikylaubetituierte B # mo1- and« ephthalineMlte. linseine examples of solohe Sturen are Bensoleulfonsänre \ P Tblttolsttlfonsäure, Xylolemlfoaeäure, Ootadeoylbenioleulfoneture, leshtb ^ lns "lfoneäar ·« nd ootjl-, dodeoyl- and hexedeoyleubeUtuierte lepntfaellneVlfosisäuren. As a precautionary measure, each and every arylous membrane uses an alkyl release element, the QrMe smeretoht. surface-active on the connection »Uceaeohnften to lending _{9 days}

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in that Genamtverfahra special with regard to isolation of high quality products is further improved »The However, the respective type of aryl sulfonic acid is not critical if only the beneficial effect as a catalyst for implementation contemplated is "benzene and naphthalenesulfonic acids with no alkyl substituents only show as salts, if any low (surface activity. Noticeable surface-active Effects set when the ring has an alkyl substituent with 3 to 18 or more carbon atoms is introduced «Special good properties result when the alkyl substituent has about 6 to 16 carbon atoms. For those according to the invention Purposes, dodecy xbenzenesulfonic acid is the preferred one Alkylarylsulfonic acid because of its surface-active properties the catalytically active salt.

The superiority of the process according to the invention is illustrated below using the reaction of benzaldehyde with 2-methylnaphthxazole, without any intention to restrict the invention to this particular reaction Warming for a period of over 40 hours only gives a 10% yield of product. Similarly, in toluene with iodine as the catalyst, a yield of less than 10 % is obtained after 24 hours of warming. In xylene with dioethylformamide as the catalyst, no product is obtained even after heating for 49 hours.

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In xylene with p-toluenesulfonic acid as a catalyst, after 49 hours it becomes so. A yield of only 22% obtained Iq xylene with a combination of dimethylformamide and p-Toluolsttlfonsäurβ as a catalyst, a yield of 90 f> or more are obtained in order to obtain such yields require above reaction times are, however, at 40 hours, "is also the Product contaminated by impurities »which cannot be removed by washing with water« To achieve * the high degree of unity required for the main use of the product, i.e. If "as an optical brightener ^ is desired, lengthy and / or costly cleaning measures must therefore be applied"

In contrast, the process according to the invention leads to yields of 90 % or more in a time of only 5 to 6 hours. In addition, products can be obtained by the process according to the invention (when using a sulfonic acid of the detergent type for the preparation of the catalyst salt) in which the impurities present are so are designed so that they can be easily removed by washing with water in order to achieve the desired degree of purity for the use of the products as optional brighteners. "

If, in the known processes, the product is separated by pouring it into water, “ 72 hours are required before the product separates out of the mixture in a filterable form ₈ while with the process according to the invention this separation is achieved in only 9 hours

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The advantages of the invention include such high yields increased product range, shorter response times and a greatly reduced time for product dilution · αβ the in water poured Misohung "

As has already been mentioned, there are those obtainable according to the invention 2-> Styrylox azo compounds important application for optical imaging lighter for a range of both natural and synthetic fabrics, for example cotton, full, silk, Hj] Pn, Polyester and the like «, you also brighten a row of synthetic plastics both in the form of fabrics and in solid pom, for example polyacrylates, polyvinyl halides and the same. In order for whitening agents to be fully effective, it is well known that they must be of high purity. A special one The advantage of the method according to the invention is that Obtain products of suitable purity for such purposes without the application of lengthy and / or laborious purification methods who the ο

The following examples illustrate the invention without restricting it in any way. Parts are based on weight

example 1 Manufacture of 2-styrylnaphth fi>. t-dJoxazoi ^%

( technical

407 parts of 22% ammonia (5 # 26 moles) were made into a mixture of 1450 parts of xylene and 1268 parts of iDdeoylbene sulfonic acid

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C, 89 Hol) given while the temperature was kept below Ao ⁰ C. Then 1354 T _e ile benzaldehyde (f2.8 moles) and 1736 parts of i-Aoetamido-2-naphthol (8.65 Hol) was added and the whole was heated to reflux Misohung "wherein water is azeotropically removed. The Rüokfluß continued at about 90 ⁰ C, and the temperature rose gradually to a constant bit-boiling Misohung of I6O to 16> ° C to. The flushing was continued for 28 hours to complete the reaction. The Reaktionemiochung was heated to 90 - 95 ⁰ C cooled and poured into 24,250 parts of water. The resulting mixture was then stirred for 9 hours, after which the product was filtered off and washed with old water. Haoh drying at 8o ° C were 209 parts * (89.6% yield) of light yellow crystal · having a purity of 99.0% - obtained (F. 127 128 ⁰ O).

Example 2
Manufacture; of 2-Sty ^ Lnaphth Eg. 1-dloxaxol

A mixture of 134 parts of xylene, 12.6 parts of dodeoylbenzenesulfonic acid (0.04 mol) and 127.2 parts of benzaldehyde 0.2 mol) was introduced with 234 parts of a solution containing 1 parts of aaonlumdodeoylbenzenesulfonate (0.32 mol), 30 7 parts of ammonium xylene sulfonate (0.15 mol), 17 * 4 parts of ammonium sulfate and 75.9 parts of water. Then 160 _v 8 parts of iA _o etamido-2-aaphthol (0.8 mol) were added, and the entire mixture was added the heated on RUokflufiteaperatur RÜckflud began at 98 ° C, and the temperature rose allafihlicL to a constant boiling Hisohung of 163 ⁰ C to, Bas ^ was under ückfluisieden

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azeotropic ar removal vosi VJa a β ar 5.5 hours foj% eeetzt. The reaction chemistry is then cooled to 90 to 95 ^° C. and poured into 2400 parts of water. They obtained mixture was filtered off for 9 hours g (β stir to Sas product Wuide, eneohlleflend old gevasohen water and dried at 80 ⁰ C. Sas product (93.4% yield) was the same in Example vie to

Ϊ Example 3

Manufacture of 2-styrylnaphthJ2.i-dioxasol

A solution of 33.5 liters of xylene and 26.2 parts of sodeoylbenzenesulphonic acid (0.08 mol) was added beforehand to 5.85 cells of ethyl alcohol (0.08 mol), so that the exothermic reaction continued at 45-5O ⁰ O, external cooling was required. 3.0 parts of sodecylbenzenesulfonic acid (0.009 mol, 40.2 parts! -aoetaaldo-2-naiithol (0 _and 2 mol) and 31.8 parts of benzaldehyde (0.3 mol) were added. heated for 5 hours at Rttck "fluSteapiratur while knife azeotropically removed Dar reflux continued at 132 ⁰ C and increased gradually to a constant boiling Mleohung of 166 ° C to ₀ was Mleohung to 90 -. 95 ° 0 cooled and 600 parts of Water poured in. The mixture obtained was adjusted to pH 9.0 to 9.5 using aqueous sodium hydroxide and stirred for 16 hours. The product was then filtered off, washed and dried (yield 82.4 %).

Example 4

Preparation of 2 "- (p" Cblogstyrjrl) naphthfe.T-dJoxazol laoh the Arbeltewalet of Example 1 were 155 TIle (f, 1 mol)

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p-Chlorotoszaldehyde with 183 Tellea (1.0 KoI) 2-methylnaphth [2,1-dJ-oacaaol ur: ig © sststo Das Pro <! iik% 2 "(p-Ohlorstyryl) naphth £ 2,1-dj-ozaaol Hurd «in 8f Jg yield as brightly gruoJLleh-gelljer fcrletalliner featatof Γ exhalten (P, 18i«! 82,5 ⁰ Oo

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The working routine of Example 1 was followed by a number of others Trying carried out, you Auigaageatoffβ and products ilnd In Table 2 listed.

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Claims (1)

P at » n thaws; r η ο h Further training of the process according to patent _o ".". then lower alkyl or alkoxy groups. Hydroxyl, carboxyl, cyano groups or halogen atoms can be substituted, alternatively evaldehyde or haphthalene aldehyde, dex can be substituted by lower "alkyl" or alkoxy groups, hydroxyl, carboxyl, cyano or iltro groups or halogen atoms, in different ways from rasseravspaltecden and an inert old solution at RUcl: fluflteeperatur with removal of the condensation water from the Heaxtionegeaieoh and recovery of the 2 »styxyloxasol formed from dearideagent, with the. Uasetsung in the presence eli ^ he sulfonic acid and a Dialkyldr.rlvate of Fomaaid or Aoetasld old lower A3.kylgrupren is carried out, characterized labeled in ζ "lohnet, the duo Veriuhren aan in the presence of a Aaaoniun- or Aa.Vnealzee © INRR Axyleulf or acid durohftthrt. 0 0 9 8 3 4/2 1 b 0